Addition products of 3.4-dehydrocyclotetramethylene sulphone



dented Aug. 4, 1942 i v e I UNITED sTA ss APATELNTQ ADDITION PRODUCTS OF3.4-DEHYDRO- CYCLOTETRAMETHYLENE SULPHONE Detlef Delis, Leverkusen-I. G.'Werk, Germany, assignor, by mesne assignments, to General Aniline &Film Corporation, New York, N. Y., a corporationof Delaware No Drawing.Original application January 21,

f Y 1938, Serial No. 186,085. Divided and this application September 25,1940, Serial No. 358,298. 3 In Germany January 22, 1937 a ,2 Claims.(c1. 260-329) -The present invention relates to new addition soluble inwater. .Inwcase polyvalentalcohols M products which are valuableintermediates and are employed one molecule of the same can re auxiliaryproducts for the textile, lacquer, dyeact with several molecules of thesulphone. U All v stuff and related industries. r such possibilities areintended to fall within] My new products are defined by'the following 5the scope of my claims. s H I formula: Amongst the amines which areobtainable inv H accordance with my present invention there arementioned as preferred members those wherein gr HC C stands for theradical of a primary amine having 1 up to 18'carbon-atoms, Thehighermembersin. .form oftheir salts with suitable-acids are valu-J ableauxiliary products for the textile industry. Q The substituents whichare connected with the.

nitrogen may also be of cyclic nature, andfin case both free bonds ofthe nitrogen aresatisfled by alkyls the latter may be connected in formwherein .1: stands for a member of the group consisting of 0, S- and ofa heterocyclic ring systemj products of the latter typeare obtained, forinstance, by the re- 1 the free bonds of which are satisfied by a memffgi s e 51111- ber of the grou consisting of hydrogen and 20 p an plpe-nn w I alkyl. These pr oducts are generally prepared It to be,undgrstqd'that the alkyls which-are by causing water, hydrogensulphide, alcohols, connected wlth the oxygen s r an m ammonia orprimary or secondary amines to'reatoms may contain various .Subsfituentsu act upon 3.4-dehydrocyclotetramethylene suldeparting from thesense 9 ypresent YF 1 phone, preferably in an alkaline medium. v In case the saidstarting material is caused to The folowmg examples illustrate myinvention react with water or hydrogen sulphide the rewithout,restricting thereto sulting hydroxyor mercaptocyclotetramethylene partsbemg by welghtz" sulphone easily reacts with another molecule of3.4-dehydrocyclotetramethylene sulphone, thus I yielding products of thetype: 120 parts of 3.4-dehydrocyclotetramethylene sulphone are suspendedin a solution of 2 parts Example "1 H of potassium hydroxide in 50 partsof water and H1CCvC stirred at ordinary temperature. .After four H20 H2Odays the'whole mixture has dissolved and after sometime Ithesol idreaction product separates. Finally thereactionliquor completelysolidifies.

Neutralization is efiected' and the reaction product melting at.'l5'7C.=is isolated. Ithas probably the following constitutiont; 1

11 being 0 or S. It is to be understood that in each case thecorresponding hydroxy or mer 40 capto compound is formed asintermediate; in

reacting with another molecule of 3.4-dehydroe H H v vcyclotetramethylene sulphone these intermedi- L I H ates act the part ofan alcchol. 1 r H CH H H Particular importance is attached to the prodg2 g I ucts wherein :1: stands for O-alkyl and among s H s a those theproducts wherein the alkyl contains 7 e I, V H n up to nine carbonatoms. The alkyl may also it being to be understood that the product oibe of a cyclic nature, it being to be understood the formula Y that thefinal products mentioned in the forego- H2d -CH.0H

ing paragraph are embraced within the scope of e I my claims. Theproducts of vthe reaction of a V i methyl alcohol, ethyl alcohol orpropyl alcohol I s are easily soluble in water, whereas the highermembers are dinicultly soluble and finally inis formed as intermediate.

Example 2 80 parts of potassium hydroxide are dissolved in 2000 parts ofmethanol. During hours at C. 4000 parts of 3.4dehydrocyclotetramethylene sulphone are added while stirring. Stirringis continued for a further 24 hours. Now first sulphuric acid is addeduntil the liquid turns Congo paper blue and then potassium or magnesiu'mcarbonate is added in excess. The sep-- arated salts are removed byfiltration and the ether which has probably the following constitution:

is obtained by distilling oil? the excess methanol. Distillation of theether in vacuo yields a colorless, odorless liquid, boiling point 164 C.under a pressure of 12.5 mm. The ether is miscible with water and mostorganic solvents.

Themethyl alcohol may be replaced'by any other alcohol. The product ofthe reaction of ethyl alcohol has the melting point C. and is alsomiscible with water. Both propyl ethers are liquid and also misciblewith water, though not in every proportion. The butyl ethers likewiserepresent liquids but are diflicultly soluble in water; the n-butylether has a boiling point 179 C.

- ethylene glycol monomethyl or monoethylether are water-soluble liquidsof the boiling point 171 or 170 C. at 3 mm. pressure. The product of thereaction of 2 mols of. 3.4-dehydrocyclotetramethylene sulphone and 1 molof ethylene glycol has a melting point 157 C. The 3.4-dehydrocyclotetramethylene sulphone may also be reacted upon with mixtures ofdifierent alcohols. In case the mixture of of 1.3-propylene glycol, ofglycerine and 25% of hexit is employed in such a proportion that 3hydroxy groups are present within each one molecule of the sulphone,there is obtained a highly viscous water-soluble reaction product.Furthermore, the mixedalcohols obtained by the catalytic hydration ofcoconut oil can'be employed; the resulting product is a solid compoundwhich cannot be distilled. in vacuo without decomposition.

With respect to the working conditions the potassium hydroxide can bereplaced by other alkaline reaction products such as sodium hydroxide oralkali metal alcoholates. The reaction temperature can vary within widelimits. Advantageously the reaction is carried out below 65 C. Therebydecomposition of the unsaturated sulphone which already becomes evidentat 80 C. is avoided. It is further advantageous to work without accessof air.

Example 3 In this example there is employed as starting material thefraction boiling between about 145-- 162-C..of the mixtures of alcoholsobtainable by causing hydrogen to react upon carbon oxide in thepresence of catalyst. In 1250 parts of this mixture of alcohols thereare dissolved20 parts of potassium hydroxide, 1000 parts ofI'M-dehydrocyclotetramethylene sulphone are gradually added thereto.After several hours stirring the sulphone has been completely dissolved,whereupon the temperature must be kept below about 30 C. by cooling.After 12 hours stirring the potassium hydroxide is neutralized, thesalts are re moved by filtration and the non-reacted alcohols I areremoved by heating in vacuo. 1800 parts of an oily reaction product areobtained which has the boiling point 192-196 at 12 mm. pressure. If

the above-mentioned fraction is replaced by the fraction boiling between160-220", an addition product of similar properties is obtained.

7 Example 4' parts of 3.4-dehydrocyclotetramethylene sulphone arestirred with a. solution of 50 parts of 62% sodium hydrosulphide in 200parts of water at 60-65 C. After two hours the separated oil solidifies.After two hours standing the mixture is cooled and the reaction productis isolated (melting point 192 0.); it has probably the 101- lowingconstitution:

it being to be understood that the product of the formula:

is formed as intermediate.

Example 5 40 parts of V 3.4 -dehydrocyclotetramethylene sulphone aredissolved together with 31 parts of thioglycolic acid in parts of waterand at- 60-70 C. 2'7 parts of sodium hydroxide are added. a

The addition reaction takes place very quickly and is finished after 4hours. The solution contains 13 parts of free sodium hydroxide.

Example 6 600 parts of 3.4-dehydrocyclotetramethylene sulphone areheated in an autoclave with 1000 parts of liquid ammonia to 65 C. After28 hours the product formed is isolated. It consists mostly of a primaryamine probably of the constitution:

H1C-CHNH1 It represents a viscous liquid easily soluble in water.

Example 7 120 parts of 3.4-dehydrocyclotetramethylene sulphone'arecaused to react with 500 parts of a 25% methylamine solution in anautoclave at 60-70 C. The reaction product chiefly consists of asecondary amine probably of the constitution:

HaC-CH.NHCH:

It represents a hygroscopic water-soluble liquid wherein a: stands fora. member of the group conwhich can be distilled in vacuo. sisting ofThe methylamine can be replaced by various alkyl other amines. Thusethanolamine yields a N highly viscous hygroscopic liquid which crystal-5 a lizes on standing. Piperidine yields 'the correyl sponding tertiaryamine which is liquid at ordi- NH-alkyl d N11 nary temperature.Dodecylamine and higher amines yield well crystallized compounds.

This application is a divisional of application 10 Ser. No. 186,085,which is now U. S. Patent No. 2,219,006, issued October 22, 1940.

. sulphone in an alkaline medium. I claim: DETLEF DELFS. 1. The productsof the formula H10 0-: H16 41H:

2. The process which comprises causing a member of the group consistingof ammonium and'lts monoand dialkyl substitution products to react upon3,4-dehydrocyclotetramethylene-

